Low temperature injection molding of polyarylene sulfide compositions

ABSTRACT

A method for injection molding a thermoplastic composition that contains a polyarylene sulfide and an aromatic amide oligomer is provided. Due to the improved crystallization properties imparted by the oligomer, the present inventors have discovered that the thermoplastic composition can be molded at lower temperatures to still achieve the same degree of crystallization. In addition to minimizing the energy requirements for the molding operation, such low mold temperatures may be accomplished using heating mediums that are less corrosive and expensive than some conventional techniques.

RELATED APPLICATIONS

This application claims filing benefit of U.S. Provisional PatentApplication Ser. No. 61/576,422 filed on Dec. 16, 2011, which isincorporated herein in its entirety.

BACKGROUND OF THE INVENTION

Polyphenylene sulfide (“PPS”) is a high performance polymer that canwithstand high thermal, chemical, and mechanical stresses. Due to itsrelatively slow crystallization rate, however, injection molding ofparts from polyphenylene sulfide can be challenging. For example, toachieve the desired degree of crystallization, molding is generallyconducted at a high mold temperature (˜130° C. or more) and for arelatively long cycle time. Unfortunately, high mold temperaturestypically dictate the need for expensive and corrosive cooling mediums(e.g., oils) in order to achieve good mechanical properties. Attempts toaddress the problems noted above have generally involved the inclusionof various additives in the polymer composition to help improve itscrystallization properties. To date, however, such attempts have notbeen fully satisfactory. As such, a need exists for a suitable methodfor injection molding polyarylene sulfide at low temperatures whilestill achieving good mechanical properties.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, a method forinjection molding a thermoplastic composition is disclosed. The methodcomprises injecting a thermoplastic composition into a mold cavity,wherein the thermoplastic composition comprises a polyarylene sulfideand aromatic amide oligomer; cooling the thermoplastic compositionwithin the mold cavity at a mold temperature of from about 50° C. toabout 120° C.; and ejecting the molded part from the mold cavity.

Other features and aspects of the present invention are set forth ingreater detail below.

BRIEF DESCRIPTION OF THE FIGURES

A full and enabling disclosure of the present invention, including thebest mode thereof to one skilled in the art, is set forth moreparticularly in the remainder of the specification, including referenceto the accompanying figures, in which:

FIG. 1 is a cross-sectional view of one embodiment of an injection moldapparatus that may be employed in the present invention;

FIG. 2 is a perspective view of an electronic device that can be formedin accordance with one embodiment of the present invention; and

FIG. 3 is a perspective view of the electronic device of FIG. 2, shownin closed configuration.

FIG. 4 illustrates a water pump that may be formed in accordance withone embodiment of the present invention.

DETAILED DESCRIPTION

It is to be understood that the terminology used herein is for thepurpose of describing particular embodiments only and is not intended tolimit the scope of the present invention.

“Alkyl” refers to monovalent saturated aliphatic hydrocarbyl groupshaving from 1 to 10 carbon atoms and, in some embodiments, from 1 to 6carbon atoms. “C_(x-y)alkyl” refers to alkyl groups having from x to ycarbon atoms. This term includes, by way of example, linear and branchedhydrocarbyl groups such as methyl (CH₃), ethyl (CH₃CH₂), n-propyl(CH₃CH₂CH₂), isopropyl ((CH₃)₂CH), n-butyl (CH₃CH₂CH2CH₂), isobutyl((CH₃)₂CHCH₂), sec-butyl ((CH₃)(CH₃CH₂)CH), t-butyl ((CH₃)₃C), n-pentyl(CH₃CH₂CH₂CH₂CH₂), and neopentyl ((CH₃)₃CCH₂).

“Alkenyl” refers to a linear or branched hydrocarbyl group having from 2to 10 carbon atoms and in some embodiments from 2 to 6 carbon atoms or 2to 4 carbon atoms and having at least 1 site of vinyl unsaturation(>C═C<). For example, (C_(x)-C_(y))alkenyl refers to alkenyl groupshaving from x to y carbon atoms and is meant to include for example,ethenyl, propenyl, 1,3-butadienyl, and so forth.

“Alkynyl” refers to refers to a linear or branched monovalenthydrocarbon radical containing at least one triple bond. The term“alkynyl” may also include those hydrocarbyl groups having other typesof bonds, such as a double bond and a triple bond.

“Aryl” refers to an aromatic group of from 3 to 14 carbon atoms and noring heteroatoms and having a single ring (e.g., phenyl) or multiplecondensed (fused) rings (e.g., naphthyl or anthryl). For multiple ringsystems, including fused, bridged, and spiro ring systems havingaromatic and non-aromatic rings that have no ring heteroatoms, the term“Aryl” applies when the point of attachment is at an aromatic carbonatom (e.g., 5,6,7,8 tetrahydronaphthalene-2-yl is an aryl group as itspoint of attachment is at the 2-position of the aromatic phenyl ring).

“Cycloalkyl” refers to a saturated or partially saturated cyclic groupof from 3 to 14 carbon atoms and no ring heteroatoms and having a singlering or multiple rings including fused, bridged, and spiro ring systems.For multiple ring systems having aromatic and non-aromatic rings thathave no ring heteroatoms, the term “cycloalkyl” applies when the pointof attachment is at a non-aromatic carbon atom (e.g.,5,6,7,8-tetrahydronaphthalene-5-yl). The term “cycloalkyl” includescycloalkenyl groups, such as adamantyl, cyclopropyl, cyclobutyl,cyclopentyl, cyclooctyl, and cyclohexenyl. The term “cycloalkenyl” issometimes employed to refer to a partially saturated cycloalkyl ringhaving at least one site of >C═C< ring unsaturation.

“Halo” or “halogen” refers to fluoro, chloro, bromo, and iodo.

“Haloalkyl” refers to substitution of alkyl groups with 1 to 5 or insome embodiments 1 to 3 halo groups.

“Heteroaryl” refers to an aromatic group of from 1 to 14 carbon atomsand 1 to 6 heteroatoms selected from oxygen, nitrogen, and sulfur andincludes single ring (e.g., imidazolyl) and multiple ring systems (e.g.,benzimidazol-2-yl and benzimidazol-6-yl). For multiple ring systems,including fused, bridged, and spiro ring systems having aromatic andnon-aromatic rings, the term “heteroaryl” applies if there is at leastone ring heteroatom and the point of attachment is at an atom of anaromatic ring (e.g., 1,2,3,4-tetrahydroquinolin-6-yl and5,6,7,8-tetrahydroquinolin-3-yl). In some embodiments, the nitrogenand/or the sulfur ring atom(s) of the heteroaryl group are optionallyoxidized to provide for the N oxide (N→O), sulfinyl, or sulfonylmoieties. Examples of heteroaryl groups include, but are not limited to,pyridyl, furanyl, thienyl, thiazolyl, isothiazolyl, triazolyl,imidazolyl, imidazolinyl, isoxazolyl, pyrrolyl, pyrazolyl, pyridazinyl,pyrimidinyl, purinyl, phthalazyl, naphthylpryidyl, benzofuranyl,tetrahydrobenzofuranyl, isobenzofuranyl, benzothiazolyl,benzoisothiazolyl, benzotriazolyl, indolyl, isoindolyl, indolizinyl,dihydroindolyl, indazolyl, indolinyl, benzoxazolyl, quinolyl,isoquinolyl, quinolizyl, quianazolyl, quinoxalyl, tetrahydroquinolinyl,isoquinolyl, quinazolinonyl, benzimidazolyl, benzisoxazolyl,benzothienyl, benzopyridazinyl, pteridinyl, carbazolyl, carbolinyl,phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenoxazinyl,phenothiazinyl, and phthalimidyl.

“Heterocyclic” or “heterocycle” or “heterocycloalkyl” or “heterocyclyl”refers to a saturated or partially saturated cyclic group having from 1to 14 carbon atoms and from 1 to 6 heteroatoms selected from nitrogen,sulfur, or oxygen and includes single ring and multiple ring systemsincluding fused, bridged, and spiro ring systems. For multiple ringsystems having aromatic and/or non-aromatic rings, the terms“heterocyclic”, “heterocycle”, “heterocycloalkyl”, or “heterocyclyl”apply when there is at least one ring heteroatom and the point ofattachment is at an atom of a non-aromatic ring (e.g.,decahydroquinolin-6-yl). In some embodiments, the nitrogen and/or sulfuratom(s) of the heterocyclic group are optionally oxidized to provide forthe N oxide, sulfinyl, sulfonyl moieties. Examples of heterocyclylgroups include, but are not limited to, azetidinyl, tetrahydropyranyl,piperidinyl, N-methylpiperidin-3-yl, piperazinyl,N-methylpyrrolidin-3-yl, 3-pyrrolidinyl, 2-pyrrolidon-1-yl, morpholinyl,thiomorpholinyl, imidazolidinyl, and pyrrolidinyl.

It should be understood that the aforementioned definitions encompassunsubstituted groups, as well as groups substituted with one or moreother functional groups as is known in the art. For example, an aryl,heteroaryl, cycloalkyl, or heterocyclyl group may be substituted withfrom 1 to 8, in some embodiments from 1 to 5, in some embodiments from 1to 3, and in some embodiments, from 1 to 2 substituents selected fromalkyl, alkenyl, alkynyl, alkoxy, acyl, acylamino, acyloxy, amino,quaternary amino, amide, imino, amidino, aminocarbonylamino,amidinocarbonylamino, aminothiocarbonyl, aminocarbonylamino,aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl,aminosulfonyloxy, aminosulfonylamino, aryl, aryloxy, arylthio, azido,carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy,cyano, cycloalkyl, cycloalkyloxy, cycloalkylthio, guanidino, halo,haloalkyl, haloalkoxy, hydroxy, hydroxyamino, alkoxyamino, hydrazino,heteroaryl, heteroaryloxy, heteroarylthio, heterocyclyl,heterocyclyloxy, heterocyclylthio, nitro, oxo, thione, phosphate,phosphonate, phosphinate, phosphonamidate, phosphorodiamidate,phosphoramidate monoester, cyclic phosphoramidate, cyclicphosphorodiamidate, phosphoramidate diester, sulfate, sulfonate,sulfonyl, substituted sulfonyl, sulfonyloxy, thioacyl, thiocyanate,thiol, alkylthio, etc., as well as combinations of such substituents.

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentinvention.

Generally speaking, the present invention is directed to a method forinjection molding a thermoplastic composition that contains apolyarylene sulfide and an aromatic amide oligomer. The presentinventors have discovered that the aromatic amide oligomer cansignificantly improve the crystallization properties of the composition,which allows it to be molded at lower temperatures while still achievingthe same degree of crystallization. For example, the mold temperature(e.g., temperature of a surface of the mold) may be from about 50° C. toabout 120° C., in some embodiments from about 60° C. to about 110° C.,and in some embodiments, from about 70° C. to about 90° C. Shortercooling cycles may also be employed. In addition to minimizing theenergy requirements for the molding operation, such low moldtemperatures and/or short cooling cycles may be accomplished usingcooling mediums that are less corrosive and expensive than someconventional techniques. For example, liquid water may be employed asthe cooling medium. Further, the use of low mold temperatures can alsodecrease the production of “flash” normally associated with hightemperature molding operations. For example, the length of any flash(also known as burrs) created during a molding operation may be about0.17 millimeters or less, in some embodiments about 0.14 millimeters orless, and in some embodiments, about 0.13 millimeters or less.

Various embodiments of the present invention will now be described ingreater detail below.

I. Thermoplastic Composition

A. Polyarylene Sulfide

As noted above, the thermoplastic composition contains at least onepolyarylene sulfide, which is generally able to withstand relativelyhigh temperatures without melting. Although the actual amount may varydepending on desired application, polyarylene sulfide(s) typicallyconstitute from about 30 wt. % to about 95 wt. %, in some embodimentsfrom about 35 wt. % to about 90 wt. %, and in some embodiments, fromabout 40 wt. % to about 80 wt. % of the thermoplastic composition. Thepolyarylene sulfide(s) generally have repeating units of the formula:—[(Ar¹)_(n)—X]_(m)—[(Ar²)_(i)—Y]_(j)—[(Ar³)_(k)—Z]_(l)—[(Ar⁴)_(o)—W]_(p)—wherein,

Ar¹, Ar², Ar³, and Ar⁴ are independently arylene units of 6 to 18 carbonatoms;

W, X, Y, and Z are independently bivalent linking groups selected from—SO₂—, —S—, —SO—, —CO—, —O—, —C(O)O— or alkylene or alkylidene groups of1 to 6 carbon atoms, wherein at least one of the linking groups is —S—;and

n, m, i, j, k, l, o, and p are independently 0, 1, 2, 3, or 4, subjectto the proviso that their sum total is not less than 2.

The arylene units Ar¹, Ar², Ar³, and Ar⁴ may be selectively substitutedor unsubstituted. Advantageous arylene units are phenylene, biphenylene,naphthylene, anthracene and phenanthrene. The polyarylene sulfidetypically include's more than about 30 mol %, more than about 50 mol %,or more than about 70 mol % arylene sulfide (—S—) units. For example,the polyarylene sulfide may include at least 85 mol % sulfide linkagesattached directly to two aromatic rings. In one particular embodiment,the polyarylene sulfide is a polyphenylene sulfide, defined herein ascontaining the phenylene sulfide structure —(C₆H₄—S)_(n)— (wherein n isan integer of 1 or more) as a component thereof.

Synthesis techniques that may be used in making a polyarylene sulfideare generally known in the art. By way of example, a process forproducing a polyarylene sulfide can include reacting a material thatprovides a hydrosulfide ion (e.g., an alkali metal sulfide) with adihaloaromatic compound in an organic amide solvent. The alkali metalsulfide can be, for example, lithium sulfide, sodium sulfide, potassiumsulfide, rubidium sulfide, cesium sulfide or a mixture thereof. When thealkali metal sulfide is a hydrate or an aqueous mixture, the alkalimetal sulfide can be processed according to a dehydrating operation inadvance of the polymerization reaction. An alkali metal sulfide can alsobe generated in situ. In addition, a small amount of an alkali metalhydroxide can be included in the reaction to remove or react impurities(e.g., to change such impurities to harmless materials) such as analkali metal polysulfide or an alkali metal thiosulfate, which may bepresent in a very small amount with the alkali metal sulfide.

The dihaloaromatic compound can be, without limitation, ano-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene,dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoicacid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenylsulfoxide or dihalodiphenyl ketone. Dihaloaromatic compounds may be usedeither singly or in any combination thereof. Specific exemplarydihaloaromatic compounds can include, without limitation,p-dichlorobenzene; m-dichlorobenzene; o-dichlorobenzene;2,5-dichlorotoluene; 1,4-dibromobenzene; 1,4-dichloronaphthalene;1-methoxy-2,5-dichlorobenzene; 4,4′-dichlorobiphenyl;3,5-dichlorobenzoic acid; 4,4′-dichlorodiphenyl ether;4,4′-dichlorodiphenylsulfone; 4,4′-dichlorodiphenylsulfoxide; and4,4′-dichlorodiphenyl ketone. The halogen atom can be fluorine,chlorine, bromine or iodine, and two halogen atoms in the samedihalo-aromatic compound may be the same or different from each other.In one embodiment, o-dichlorobenzene, m-dichlorobenzene,p-dichlorobenzene or a mixture of two or more compounds thereof is usedas the dihalo-aromatic compound. As is known in the art, it is alsopossible to use a monohalo compound (not necessarily an aromaticcompound) in combination with the dihaloaromatic compound in order toform end groups of the polyarylene sulfide or to regulate thepolymerization reaction and/or the molecular weight of the polyarylenesulfide.

The polyarylene sulfide(s) may be homopolymers or copolymers. Forinstance, selective combination of dihaloaromatic compounds can resultin a polyarylene sulfide copolymer containing not less than twodifferent units. For instance, when p-dichlorobenzene is used incombination with m-dichlorobenzene or 4,4′-dichlorodiphenylsulfone, apolyarylene sulfide copolymer can be formed containing segments havingthe structure of formula:

and segments having the structure of formula:

or segments having the structure of formula:

In another embodiment, a polyarylene sulfide copolymer may be formedthat includes a first segment with a number-average molar mass Mn offrom 1000 to 20,000 g/mol. The first segment may include first unitsthat have been derived from structures of the formula:

where the radicals R¹ and R², independently of one another, are ahydrogen, fluorine, chlorine or bromine atom or a branched or unbranchedalkyl or alkoxy radical having from 1 to 6 carbon atoms; and/or secondunits that are derived from structures of the formula:

The first unit may be p-hydroxybenzoic acid or one of its derivatives,and the second unit may be composed of 2-hydroxynaphthalene-6-carboxylicacid. The second segment may be derived from a polyarylene sulfidestructure of the formula:—[Ar—S]_(q)—

where Ar is an aromatic radical, or more than one condensed aromaticradical, and q is a number from 2 to 100, in particular from 5 to 20.The radical Ar may be a phenylene or naphthylene radical. In oneembodiment, the second segment may be derived frompoly(m-thiophenylene), from poly(o-thiophenylene), or frompoly(p-thiophenylene).

The polyarylene sulfide(s) may be linear, semi-linear, branched orcrosslinked. Linear polyarylene sulfides typically contain 80 mol % ormore of the repeating unit —(Ar—S)—. Such linear polymers may alsoinclude a small amount of a branching unit or a cross-linking unit, butthe amount of branching or cross-linking units is typically less thanabout 1 mol % of the total monomer units of the polyarylene sulfide. Alinear polyarylene sulfide polymer may be a random copolymer or a blockcopolymer containing the above-mentioned repeating unit. Semi-linearpolyarylene sulfides may likewise have a cross-linking structure or abranched structure introduced into the polymer a small amount of one ormore monomers having three or more reactive functional groups. By way ofexample, monomer components used in forming a semi-linear polyarylenesulfide can include an amount of polyhaloaromatic compounds having twoor more halogen substituents per molecule which can be utilized inpreparing branched polymers. Such monomers can be represented by theformula R′X_(n), where each X is selected from chlorine, bromine, andiodine, n is an integer of 3 to 6, and R′ is a polyvalent aromaticradical of valence n which can have up to about 4 methyl substituents,the total number of carbon atoms in R′ being within the range of 6 toabout 16. Examples of some polyhaloaromatic compounds having more thantwo halogens substituted per molecule that can be employed in forming asemi-linear polyarylene sulfide include 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene,1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene,1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2′,4,4′-tetrachlorobiphenyl,2,2′,5,5′-tetra-iodobiphenyl,2,2′,6,6′-tetrabromo-3,3′,5,5′-tetramethylbiphenyl,1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene,etc., and mixtures thereof.

Regardless of the particular structure, the number average molecularweight of the polyarylene sulfide is typically about 15,000 g/mol ormore, and in some embodiments, about 30,000 g/mol or more. In certaincases, a small amount of chlorine may be employed during formation ofthe polyarylene sulfide. Nevertheless, the polyarylene sulfide willstill have a low chlorine content, such as about 1000 ppm or less, insome embodiments about 900 ppm or less, in some embodiments from about 1to about 800 ppm, and in some embodiments, from about 2 to about 700ppm. In certain embodiments, however, the polyarylene sulfide isgenerally free of chlorine or other halogens.

B. Aromatic Amide Oligomer

Aromatic amide oligomers typically constitute from about 0.1 wt. % toabout 8 wt. %, in some embodiments from about 0.2 wt. % to about 4 wt.%, and in some embodiments, from about 0.5 wt. % to about 2.5 wt. % ofthe thermoplastic composition. The aromatic amide oligomer generally hasa relatively low molecular weight so that it can aid in reducing highshear viscosity and also improve the crystallization properties of thepolyarylene sulfide. For example, the oligomer typically has a molecularweight of about 3,000 grams per mole or less, in some embodiments fromabout 50 to about 2,000 grams per mole, in some embodiments from about100 to about 1,500 grams per mole, and in some embodiments, from about200 to about 1,200 grams per mole.

In addition to possessing a relatively low molecular weight, theoligomer also generally possesses a high amide functionality. Withoutintending to be limited by theory, it is believed that active hydrogenatoms of the amide functional groups are capable of forming a hydrogenbond with the backbone of polyarylene sulfides. Such hydrogen bondingstrengthens the attachment of the oligomer to the polyarylene sulfidematrix and thus minimizes the likelihood that it becomes volatilizedduring compounding, molding, and/or use. This minimizes off-gassing andthe formation of blisters that would otherwise impact the finalmechanical properties of a part made from the polymer composition. Thedegree of amide functionality for a given molecule may be characterizedby its “amide equivalent weight”, which reflects the amount of acompound that contains one molecule of an amide functional group and maybe calculated by dividing the molecular weight of the compound by thenumber of amide groups in the molecule. For example, the aromatic amideoligomer may contain from 1 to 15, in some embodiments from 2 to 10, andin some embodiments, from 2 to 8 amide functional groups per molecule.The amide equivalent weight may likewise be from about 10 to about 1,000grams per mole or less, in some embodiments from about 50 to about 500grams per mole, and in some embodiments, from about 100 to about 300grams per mole.

While providing the benefits noted, the aromatic amide oligomer does notgenerally react with the polymer backbone of the polyarylene sulfide toany appreciable extent so that the mechanical properties of the polymerare not adversely impacted. To help better minimize reactivity, theoligomer typically contains a core formed from one or more aromaticrings (including heteroaromatic). The oligomer may also contain terminalgroups formed from one or more aromatic rings. Such an “aromatic”oligomer thus possesses little, if any, reactivity with the basepolymer. For example, one embodiment of such an aromatic amide oligomeris provided below in Formula (I):

wherein,

ring B is a 6-membered aromatic ring wherein 1 to 3 ring carbon atomsare optionally replaced by nitrogen or oxygen, wherein each nitrogen isoptionally oxidized, and wherein ring B may be optionally fused orlinked to a 5- or 6-membered aryl, heteroaryl, cycloalkyl, orheterocyclyl;

R₅ is halo, haloalkyl, alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, orheterocyclyl;

m is from 0 to 4;

X₁ and X₂ are independently C(O)HN or NHC(O); and

R₁ and R₂ are independently selected from aryl, heteroaryl, cycloalkyl,and heterocyclyl.

In certain embodiments, Ring B may be selected from the following:

wherein,

m is 0, 1, 2, 3, or 4, in some embodiments m is 0, 1, or 2, in someembodiments m is 0 or 1, and in some embodiments, m is 0; and

R₅ is halo, haloalkyl, alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, orheterocyclyl. Ring B may be phenyl.

In certain embodiments, the oligomer is a di-functional compound in thatRing B is directly bonded to only two (2) amide groups (e.g., C(O)HN orNHC(O)). In such embodiments, m in Formula (I) may be 0. Of course, incertain embodiments, Ring B may also be directly bonded to three (3) ormore amide groups. For example, one embodiment of such a compound isprovided by general formula (II):

wherein,

ring B, R₅, X₁, X₂, R₁, and R₂ are as defined above;

m is from 0 to 3;

X₃ is C(O)HN or NHC(O); and

R₃ is selected from aryl, heteroaryl, cycloalkyl, and heterocyclyl.

Another embodiment of such a compound is provided by general formula(III):

wherein,

ring B, R₅, X₁, X₂, X₃, R₁, R₂, and R₃ are as defined above;

X₄ is C(O)HN or NHC(O); and

R₄ is selected from aryl, heteroaryl, cycloalkyl, and heterocyclyl.

In some embodiments, R₁, R₂, R₃, and/or R₄ in the structures noted abovemay be selected from the following:

wherein,

n is 0, 1, 2, 3, 4, or 5, in some embodiments n is 0, 1, or 2, and insome embodiments, n is 0 or 1; and

R₆ is halo, haloalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, or heterocyclyl.

In one particular embodiment, the aromatic amide oligomer has thefollowing general formula (IV):

wherein,

X₁ and X₂ are independently C(O)HN or NHC(O);

R₅, R₇, and R₈ are independently selected from halo, haloalkyl, alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;

m is from 0 to 4; and

p and q are independently from 0 to 5.

In another embodiment, the aromatic amide oligomer has the followinggeneral formula (V):

wherein,

X₁, X₂, R₅, R₇, R₈, m, p, and q are as defined above.

For example, in certain embodiments, m, p, and q in Formula (IV) andFormula (V) may be equal to 0 so that the core and terminal aromaticgroups are unsubstituted. In other embodiments, m may be 0 and p and qmay be from 1 to 5. In such embodiments, for example, R₇ and/or R₈ maybe halo (e.g., fluorine). In other embodiments, R₇ and/or R₈ may be aryl(e.g., phenyl) or aryl substituted with an amide group having thestructure: —C(O)R₁₂N— or —NR₁₃C(O)—, wherein R₁₂ and R₁₃ areindependently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, and heterocyclyl. In one particular embodiment,for example, R₆ and/or R₇ are phenyl substituted with —C(O)HN— or—NHC(O)—. In yet other embodiments, R₇ and/or R₈ may be heteroaryl(e.g., pyridinyl).

In yet another embodiment, the aromatic amide oligomer has the followinggeneral formula (VI):

wherein,

X₁, X₂, and X₃ are independently C(O)HN or NHC(O);

R₅, R₇, R₈, and R₉ are independently selected from halo, haloalkyl,alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;

m is from 0 to 3; and

p, q, and r are independently from 0 to 5.

In yet another embodiment, the aromatic amide oligomer has the followinggeneral formula (VII):

wherein,

X₁, X₂, X₃, R₅, R₇, R₈, R₉, m, p, q, and r are as defined above.

For example, in certain embodiments, m, p, q, and r in Formula (VI) orin Formula (VII) may be equal to 0 so that the core and terminalaromatic groups are unsubstituted. In other embodiments, m may be 0 andp, q, and r may be from 1 to 5. In such embodiments, for example, R₇,R₈, and/or R₉ may be halo (e.g., fluorine). In other embodiments, R₇,R₈, and/or R₉ may be aryl (e.g., phenyl) or aryl substituted with anamide group having the structure: —C(O)R₁₂N— or —NR₁₃C(O)—, wherein R₁₂and R₁₃ are independently selected from hydrogen, alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl. In oneparticular embodiment, for example, R₇, R₈, and/or R₉ are phenylsubstituted with —C(O)HN— or —NHC(O)—. In yet other embodiments, R₇, R₈,and/or R₉ may be heteroaryl (e.g., pyridinyl).

Specific embodiments of the aromatic amide oligomer of the presentinvention are also set forth in the table below:

Cmpd # Structure Name A

N1,N4- diphenyl- terephthalamide B

N1,N4- diphenyl- isoterephthalamide C

N1,N4-bis(2,3,4,5,6- pentafluorophenyl) terephthalamide D

N1,N4-bis(4- benzamidophenyl) terephthalamide E

N4-phenyl-N1-[4-[[4- (phenylcarbamoyl) benzoyl] amino]phenyl]terephthalamide F1

N4-phenyl-N1-[3-[[4- (phenylcarbamoyl) benzoyl] amino]phenyl]terephthalamide F2

N1,N3-bis(4- benzamidophenyl) benzene- 1,3-dicarboxamide G1

N3-phenyl-N1-[3-[[3- (phenylcarbamoyl) benzoyl] amino]phenyl]benzene-1,3- dicarboxamide G2

N1,N3-bis(3- benzamidophenyl) benzene- 1,3-dicarboxamide H

N1,N4-bis(4- pyridyl) terephthalamide I

N1,N3-bis(4- phenylphenyl) benzene-1,3- dicarboxamide J

N1,N3,N5- triphenylbenzene- 1,3,5-tricarboxamide K

N1,N3,N5-tris(4- benzamidophenyl) benzene- 1,3,5-tricarboxamide L

N-(4,6- dibenzamido-1,3,5- triazin-2-yl) benzamide M1

N2,N7- dicyclohexyl- naphthalene-2,7- dicarboxamide M2

N2,N6- dicyclohexyl- naphthalene-2,6- dicarboxamide N

N1,N3,N5-tris(3- benzamidophenyl) benzene- 1,3,5-tricarboxamide O1

N,N′- dicyclohexyl- isoterephthalamide O2

N,N′- dicyclohexyl- terephthalamide

C. Other Additives

In addition to aromatic amide oligomers and polyarylene sulfides, thethermoplastic composition may also contain a variety of other differentcomponents to help improve its overall properties. In certainembodiments, for example, a nucleating agent may be employed inconjunction with the aromatic amide oligomer to further enhance thecrystallization properties of the composition. One example of such anucleating agent is an inorganic crystalline compound, such asboron-containing compounds (e.g., boron nitride, sodium tetraborate,potassium tetraborate, calcium tetraborate, etc.), alkaline earth metalcarbonates (e.g., calcium magnesium carbonate), oxides (e.g., titaniumoxide, aluminum oxide, magnesium oxide, zinc oxide, antimony trioxide,etc.), silicates (e.g., talc, sodium-aluminum silicate, calciumsilicate, magnesium silicate, etc.), salts of alkaline earth metals(e.g., calcium carbonate, calcium sulfate, etc.), and so forth. Boronnitride (BN) has been found to be particularly beneficial when employedin the thermoplastic composition of the present invention. Boron nitrideexists in a variety of different crystalline forms (e.g.,h-BN—hexagonal, c-BN—cubic or spharlerite, and w-BN—wurtzite), any ofwhich can generally be employed in the present invention. The hexagonalcrystalline form is particularly suitable due to its stability andsoftness.

When employed, the weight ratio of aromatic amide oligomers to inorganiccrystalline compounds is typically from about 0.8 to about 20, in someembodiments from about 1 to about 10, and in some embodiments, fromabout 1.5 to about 5. For example, aromatic amide oligomers mayconstitute from about 40 wt. % to about 95 wt. %, in some embodimentsfrom about 50 wt. % to about 90 wt %, and in some embodiments, fromabout 60 wt. % to about 80 wt % of the combined weight of the oligomersand inorganic crystalline compounds. Likewise, inorganic crystallinecompounds may constitute from about 5 wt. % to about 60 wt. %, in someembodiments from about 10 wt. % to about 50 wt. %, and in someembodiments, from about 20 wt. % to about 40 wt. % of the combinedweight of the oligomers and inorganic crystalline compounds, as well asfrom about 0.01 wt. % to about 6 wt. %, in some embodiments from about0.05 wt. % to about 3 wt. %, and in some embodiments, from about 0.1 wt.% to about 2 wt. % of the thermoplastic composition.

Another suitable additive that may be employed to improve the mechanicalproperties of the composition is an impact modifier. Examples ofsuitable impact modifiers may include, for instance, polyepoxides,polyurethanes, polybutadiene, acrylonitrile-butadiene-styrene,polysiloxanes etc., as well as mixtures thereof. In one particularembodiment, a polyepoxide modifier is employed that contains at leasttwo oxirane rings per molecule. The polyepoxide may be a linear orbranched, homopolymer or copolymer (e.g., random, graft, block, etc.)containing terminal epoxy groups, skeletal oxirane units, and/or pendentepoxy groups. The monomers employed to form such polyepoxides may vary.In one particular embodiment, for example, the polyepoxide modifiercontains at least one epoxy-functional (meth)acrylic monomericcomponent. The term “(meth)acrylic” includes acrylic and methacrylicmonomers, as well as salts or esters thereof, such as acrylate andmethacrylate monomers. Suitable epoxy-functional (meth)acrylic monomersmay include, but are not limited to, those containing 1,2-epoxy groups,such as glycidyl acrylate and glycidyl methacrylate. Other suitableepoxy-functional monomers include allyl glycidyl ether, glycidylethacrylate, and glycidyl itoconate.

If desired, additional monomers may also be employed in the polyepoxideto help achieve the desired melt viscosity. Such monomers may vary andinclude, for example, ester monomers, (meth)acrylic monomers, olefinmonomers, amide monomers, etc. In one particular embodiment, forexample, the polyepoxide modifier includes at least one linear orbranched α-olefin monomer, such as those having from 2 to 20 carbonatoms and preferably from 2 to 8 carbon atoms. Specific examples includeethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene;1-pentene; 1-pentene with one or more methyl, ethyl or propylsubstituents; 1-hexene with one or more methyl, ethyl or propylsubstituents; 1-heptene with one or more methyl, ethyl or propylsubstituents; 1-octene with one or more methyl, ethyl or propylsubstituents; 1-nonene with one or more methyl, ethyl or propylsubstituents; ethyl, methyl or dimethyl-substituted 1-decene;1-dodecene; and styrene. Particularly desired α-olefin comonomers areethylene and propylene. In one particularly desirable embodiment of thepresent invention, the polyepoxide modifier is a copolymer formed froman epoxy-functional (meth)acrylic monomeric component and α-olefinmonomeric component. For example, the polyepoxide modifier may bepoly(ethylene-co-glycidyl methacrylate). One specific example of asuitable polyepoxide modifier that may be used in the present inventionis commercially available from Arkema under the name Lotader® AX8840.Lotader® AX8950 has a melt flow rate of 5 g/10 min and has a glycidylmethacrylate monomer content of 8 wt. %.

Still another suitable additive that may be employed to improve themechanical properties of the thermoplastic composition is anorganosilane coupling agent. The coupling agent may, for example, be anyalkoxysilane coupling agent as is known in the art, such asvinlyalkoxysilanes, epoxyalkoxysilanes, aminoalkoxysilanes,mercaptoalkoxysilanes, and combinations thereof. Aminoalkoxysilanecompounds typically have the formula: R⁵—Si—(R⁶)₃, wherein R⁵ isselected from the group consisting of an amino group such as NH₂; anaminoalkyl of from about 1 to about 10 carbon atoms, or from about 2 toabout 5 carbon atoms, such as aminomethyl, aminoethyl, aminopropyl,aminobutyl, and so forth; an alkene of from about 2 to about 10 carbonatoms, or from about 2 to about 5 carbon atoms, such as ethylene,propylene, butylene, and so forth; and an alkyne of from about 2 toabout 10 carbon atoms, or from about 2 to about 5 carbon atoms, such asethyne, propyne, butyne and so forth; and wherein R⁶ is an alkoxy groupof from about 1 to about 10 atoms, or from about 2 to about 5 carbonatoms, such as methoxy, ethoxy, propoxy, and so forth. In oneembodiment, R⁵ is selected from the group consisting of aminomethyl,aminoethyl, aminopropyl, ethylene, ethyne, propylene and propyne, and R⁶is selected from the group consisting of methoxy groups, ethoxy groups,and propoxy groups. In another embodiment, R⁵ is selected from the groupconsisting of an alkene of from about 2 to about 10 carbon atoms such asethylene, propylene, butylene, and so forth, and an alkyne of from about2 to about 10 carbon atoms such as ethyne, propyne, butyne and so forth,and R⁶ is an alkoxy group of from about 1 to about 10 atoms, such asmethoxy group, ethoxy group, propoxy group, and so forth. A combinationof various aminosilanes may also be included in the mixture.

Some representative examples of aminosilane coupling agents that may beincluded in the mixture include aminopropyl triethoxysilane, aminoethyltriethoxysilane, aminopropyl trimethoxysilane, aminoethyltrimethoxysilane, ethylene trimethoxysilane, ethylene triethoxysilane,ethyne trimethoxysilane, ethyne triethoxysilane,aminoethylaminopropyltrimethoxysilane, 3-aminopropyl triethoxysilane,3-aminopropyl trimethoxysilane, 3-aminopropyl methyl dimethoxysilane or3-aminopropyl methyl diethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyl trimethoxysilane,N-phenyl-3-aminopropyl trimethoxysilane,bis(3-aminopropyl)tetramethoxysilane, bis(3-aminopropyl)tetraethoxydisiloxane, and combinations thereof. The amino silane may also be anaminoalkoxysilane, such as γ-aminopropyltrimethoxysilane,aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane,γ-diallylaminopropyltrimethoxysilane andγ-diallylaminopropyltrimethoxysilane. One suitable amino silane is3-aminopropyltriethoxysilane which is available from Degussa, SigmaChemical Company, and Aldrich Chemical Company.

Fillers may also be employed in the thermoplastic composition to helpachieve the desired properties and/or color. When employed, such mineralfillers typically constitute from about 5 wt. % to about 60 wt. %, insome embodiments from about 10 wt. % to about 50 wt. %, and in someembodiments, from about 15 wt. % to about 45 wt. % of the thermoplasticcomposition. Clay minerals may be particularly suitable for use in thepresent invention. Examples of such clay minerals include, for instance,talc (Mg₃Si₄O₁₀(OH)₂), halloysite (Al₂Si₂O₅(OH)₄), kaolinite(Al₂Si₂O₅(OH)₄), illite ((K,H₃O)(Al,Mg,Fe)₂ (Si,Al)₄O₁₀[(OH)₂,(H₂O)]),montmorillonite (Na,Ca)_(0.33)(Al,Mg)₂Si₄O₁₀(OH)₂.nH₂O), vermiculite((MgFe,Al)₃(Al,Si)₄O₁₀(OH)₂.4H₂O), palygorskite((Mg,Al)₂Si₄O₁₀(OH).4(H₂O)), pyrophyllite (Al₂Si₄O₁₀(OH)₂), etc., aswell as combinations thereof. In lieu of, or in addition to, clayminerals, still other mineral fillers may also be employed. For example,other suitable silicate fillers may also be employed, such as calciumsilicate, aluminum silicate, mica, diatomaceous earth, wollastonite, andso forth. Mica, for instance, may be a particularly suitable mineral foruse in the present invention. There are several chemically distinct micaspecies with considerable variance in geologic occurrence, but all haveessentially the same crystal structure. As used herein, the term “mica”is meant to generically include any of these species, such as muscovite(KAl₂(AlSi₃)O₁₀(OH)₂), biotite (K(Mg,Fe)₃(AlSi₃)O₁₀(OH)₂), phlogopite(KMg₃(AlSi₃)O₁₀(OH)₂), lepidolite (K(Li,Al)₂₋₃(AlSi₃)O₁₀(OH)₂),glauconite (K,Na)(Al,Mg,Fe)₂(Si,Al)₄O₁₀(OH)₂), etc., as well ascombinations thereof.

Fibrous fillers may also be employed in the thermoplastic composition.When employed, such fibrous fillers typically constitute from about 5wt. % to about 60 wt. %, in some embodiments from about 10 wt. % toabout 50 wt. %, and in some embodiments, from about 15 wt. % to about 45wt. % of the thermoplastic composition. The fibrous fillers may includeone or more fiber types including, without limitation, polymer fibers,glass fibers, carbon fibers, metal fibers, and so forth, or acombination of fiber types. In one embodiment, the fibers may be choppedglass fibers or glass fiber ravings (tows). Fiber diameters can varydepending upon the particular fiber used and are available in eitherchopped or continuous form. The fibers, for instance, can have adiameter of less than about 100 μm, such as less than about 50 μm. Forinstance, the fibers can be chopped or continuous fibers and can have afiber diameter of from about 5 μm to about 50 μm, such as from about 5μm to about 15 μm.

Lubricants may also be employed in the thermoplastic composition thatare capable of withstanding the processing conditions of poly(arylenesulfide) (typically from about 290° C. to about 320° C.) withoutsubstantial decomposition. Exemplary of such lubricants include fattyacids esters, the salts thereof, esters, fatty acid amides, organicphosphate esters, and hydrocarbon waxes of the type commonly used aslubricants in the processing of engineering plastic materials, includingmixtures thereof. Suitable fatty acids typically have a backbone carbonchain of from about 12 to about 60 carbon atoms, such as myristic acid,palmitic acid, stearic acid, arachic acid, montanic acid, octadecinicacid, parinric acid, and so forth. Suitable esters include fatty acidesters, fatty alcohol esters, wax esters, glycerol esters, glycol estersand complex esters. Fatty acid amides include fatty primary amides,fatty secondary amides, methylene and ethylene bisamides andalkanolamides such as, for example, palmitic acid amide, stearic acidamide, oleic acid amide, N,N′-ethylenebisstearamide and so forth. Alsosuitable are the metal salts of fatty acids such as calcium stearate,zinc stearate, magnesium stearate, and so forth; hydrocarbon waxes,including paraffin waxes, polyolefin and oxidized polyolefin waxes, andmicrocrystalline waxes. Particularly suitable lubricants are acids,salts, or amides of stearic acid, such as pentaerythritol tetrastearate,calcium stearate, or N,N′-ethylenebisstearamide. When employed, thelubricant(s) typically constitute from about 0.05 wt. % to about 1.5 wt.%, and in some embodiments, from about 0.1 wt. % to about 0.5 wt. % ofthe thermoplastic composition.

Still another additive that may be employed in the thermoplasticcomposition is a disulfide compound. Without wishing to be bound by anyparticular theory, the disulfide compound can undergo a polymer scissionreaction with a polyarylene sulfide during melt processing that evenfurther lowers the overall melt viscosity of the composition. Whenemployed, disulfide compounds typically constitute from about 0.01 wt. %to about 3 wt. %, in some embodiments from about 0.02 wt. % to about 1wt. %, and in some embodiments, from about 0.05 wt. % to about 0.5 wt. %of the composition. The ratio of the amount of the polyarylene sulfideto the amount of the disulfide compound may likewise be from about1000:1 to about 10:1, from about 500:1 to about 20:1, or from about400:1 to about 30:1. Suitable disulfide compounds are typically thosehaving the following formula:R³—S—S—R⁴

wherein R³ and R⁴ may be the same or different and are hydrocarbongroups that independently include from 1 to about 20 carbons. Forinstance, R³ and R⁴ may be an alkyl, cycloalkyl, aryl, or heterocyclicgroup. In certain embodiments, R³ and R⁴ are generally nonreactivefunctionalities, such as phenyl, naphthyl, ethyl, methyl, propyl, etc.Examples of such compounds include diphenyl disulfide, naphthyldisulfide, dimethyl disulfide, diethyl disulfide, and dipropyldisulfide. R³ and R⁴ may also include reactive functionality at terminalend(s) of the disulfide compound. For example, at least one of R³ and R⁴may include a terminal carboxyl group, hydroxyl group, a substituted ornon-substituted amino group, a nitro group, or the like. Examples ofcompounds may include, without limitation, 2,2′-diaminodiphenyldisulfide, 3,3′-diaminodiphenyl disulfide, 4,4′-diaminodiphenyldisulfide, dibenzyl disulfide, dithiosalicyclic acid, dithioglycolicacid, α,α′-dithiodilactic acid, β,β′-dithiodilactic acid,3,3′-dithiodipyridine, 4,4′dithiomorpholine,2,2′-dithiobis(benzothiazole), 2,2′-dithiobis(benzimidazole),2,2′-dithiobis(benzoxazole) and 2-(4′-morpholinodithio)benzothiazole.

Still other additives that can be included in the composition mayinclude, for instance, antimicrobials, pigments, antioxidants,stabilizers, surfactants, waxes, flow promoters, solid solvents, andother materials added to enhance properties and processability.

The manner in which the aromatic amide oligomer, polyarylene sulfide,and other optional additives are combined may vary as is known in theart. For instance, the materials may be supplied either simultaneouslyor in sequence to a melt processing device that dispersively blends thematerials. Batch and/or continuous melt processing techniques may beemployed. For example, a mixer/kneader, Banbury mixer, Farrel continuousmixer, single-screw extruder, twin-screw extruder, roll mill, etc., maybe utilized to blend and melt process the materials. One particularlysuitable melt processing device is a co-rotating, twin-screw extruder(e.g., Leistritz co-rotating fully intermeshing twin screw extruder).Such extruders may include feeding and venting ports and provide highintensity distributive and dispersive mixing. For example, thepolyarylene sulfide and oligomer may be fed to the same or differentfeeding ports of a twin-screw extruder and melt blended to form asubstantially homogeneous melted mixture. Melt blending may occur underhigh shear/pressure and heat to ensure sufficient dispersion. Forexample, melt processing may occur at a temperature of from about 50° C.to about 500° C., and in some embodiments, from about 100° C. to about250° C. Likewise, the apparent shear rate during melt processing mayrange from about 100 seconds⁻¹ to about 10,000 seconds⁻¹, and in someembodiments, from about 500 seconds⁻¹ to about 1,500 seconds⁻¹. Ofcourse, other variables, such as the residence time during meltprocessing, which is inversely proportional to throughput rate, may alsobe controlled to achieve the desired degree of homogeneity.

Besides melt blending, other techniques may also be employed to combinethe aromatic amide oligomer and the polyarylene sulfide. For example,the oligomer may be supplied during one or more stages of thepolymerization of the polyarylene sulfide, such as to the polymerizationapparatus. Although it may be introduced at any time, it is typicallydesired to apply the oligomer before polymerization has been initiated,and typically in conjunction with the precursor monomers for thepolyarylene sulfide. The reaction mixture is generally heated to anelevated temperature within the polymerization reactor vessel toinitiate melt polymerization of the reactants.

Regardless of the manner in which they are combined together, the degreeand rate of crystallization may be significantly enhanced by thenucleation system of the present invention. For example, thecrystallization potential of the thermoplastic composition (prior tomolding) may be about 55% or more, in some embodiments about 65% ormore, in some embodiments about 70% or more, and in some embodiments,from about 75% to about 95%. The crystallization potential may bedetermined by subtracting the latent heat of crystallization (ΔH_(c))from the latent heat of fusion (ΔH_(f)), dividing this difference by thelatent heat of fusion, and then multiplying by 100. The latent heat offusion (ΔH_(f)) and latent heat of crystallization (ΔH_(c)) may bedetermined by Differential Scanning calorimetry (“DSC”) as is well knownin the art and in accordance with ISO Standard 10350. The latent heat ofcrystallization may, for example, be about 15 Joules per gram (“J/g”) orless, in some embodiments about 12 J/g or less, in some embodimentsabout 8 J/g or less, and in some embodiments, from about 1 to about 5J/g. The latent heat of fusion may likewise be about 15 Joules per gram(“J/g”) or more, in some embodiments about 20 J/g or more, in someembodiments about 22 J/g or more, and in some embodiments, from about 22to about 28 J/g.

In addition, the thermoplastic composition may also crystallize at alower temperature than would otherwise occur absent the presence of thearomatic amide oligomer. For example, the crystallization temperature(prior to molding) of the thermoplastic composition may about 250° C. orless, in some embodiments from about 100° C. to about 245° C., and insome embodiments, from about 150° C. to about 240° C. The meltingtemperature of the thermoplastic composition may also range from about250° C. to about 320° C., and in some embodiments, from about 260° C. toabout 300° C. The melting and crystallization temperatures may bedetermined as is well known in the art using differential scanningcalorimetry in accordance with ISO Test No. 11357. Even at such meltingtemperatures, the ratio of the deflection temperature under load(“DTUL”), a measure of short term heat resistance, to the meltingtemperature may still remain relatively high. For example, the ratio mayrange from about 0.65 to about 1.00, in some embodiments from about 0.70to about 0.99, and in some embodiments, from about 0.80 to about 0.98.The specific DTUL values may, for instance, range from about 230° C. toabout 300° C., in some embodiments from about 240° C. to about 290° C.,and in some embodiments, from about 250° C. to about 280° C. Such highDTUL values can, among other things, allow the use of high speedprocesses often employed during the manufacture of components having asmall dimensional tolerance.

The present inventors have also discovered that the thermoplasticcomposition may possess a relatively low melt viscosity, which allows itto readily flow into the mold cavity during production of the part. Forinstance, the composition may have a melt viscosity of about 20 poise orless, in some embodiments about 15 poise or less, and in someembodiments, from about 0.1 to about 10 poise, as determined by acapillary rheometer at a temperature of 316° C. and shear rate of 1200seconds⁻¹. Among other things, these viscosity properties can allow thecomposition to be readily injection molded into parts having very smalldimensions without producing excessive amounts of flash.

The thermoplastic composition of the present invention has also beenfound to possess excellent mechanical properties. For example, thecomposition may possess a high impact strength, which is useful whenforming small parts. The composition may, for instance, possess an Izodnotched impact strength greater than about 4 kJ/m², in some embodimentsfrom about 5 to about 40 kJ/m², and in some embodiments, from about 6 toabout 30 kJ/m², measured at 23° C. according to ISO Test No. 180)(technically equivalent to ASTM D256, Method A). The tensile andflexural mechanical properties of the composition are also good. Forexample, the thermoplastic composition may exhibit a tensile strength offrom about 20 to about 500 MPa, in some embodiments from about 50 toabout 400 MPa, and in some embodiments, from about 100 to about 350 MPa;a tensile break strain of about 0.5% or more, in some embodiments fromabout 0.6% to about 10%, and in some embodiments, from about 0.8% toabout 3.5%; and/or a tensile modulus of from about 5,000 MPa to about25,000 MPa, in some embodiments from about 8,000 MPa to about 22,000MPa, and in some embodiments, from about 10,000 MPa to about 20,000 MPa.The tensile properties may be determined in accordance with ISO Test No.527 (technically equivalent to ASTM D638) at 23° C. The thermoplasticcomposition may also exhibit a flexural strength of from about 20 toabout 500 MPa, in some embodiments from about 50 to about 400 MPa, andin some embodiments, from about 100 to about 350 MPa; a flexural breakstrain of about 0.5% or more, in some embodiments from about 0.6% toabout 10%, and in some embodiments, from about 0.8% to about 3.5%;and/or a flexural modulus of from about 5,000 MPa to about 25,000 MPa,in some embodiments from about 8,000 MPa to about 22,000 MPa, and insome embodiments, from about 10,000 MPa to about 20,000 MPa. Theflexural properties may be determined in accordance with ISO Test No.178 (technically equivalent to ASTM D790) at 23° C.

II. Injection Molding

As indicated above, the thermoplastic composition of the presentinvention is particularly well suited for use in injection moldingoperations. For example, as is known in the art, injection can occur intwo main phases—i.e., an injection phase and holding phase. During theinjection phase, the mold cavity is completely filled with the moltenthermoplastic composition. The holding phase is initiated aftercompletion of the injection phase in which the holding pressure iscontrolled to pack additional material into the cavity and compensatefor volumetric shrinkage that occurs during cooling. After the shot hasbuilt, it can then be cooled. Once cooling is complete, the moldingcycle is completed when the mold opens and the part is ejected, such aswith the assistance of ejector pins within the mold.

Any suitable injection molding equipment may generally be employed inthe present invention. Referring to FIG. 1, for example, one embodimentof an injection molding apparatus or tool 10 that may be employed in thepresent invention is shown. In this embodiment, the apparatus 10includes a first mold base 12 and a second mold base 14, which togetherdefine an article or component-defining mold cavity 16. The moldingapparatus 10 also includes a resin flow path that extends from an outerexterior surface 20 of the first mold half 12 through a sprue 22 to amold cavity 16. The resin flow path may also include a runner and agate, both of which are not shown for purposes of simplicity. Thethermoplastic composition may be supplied to the resin flow path using avariety of techniques. For example, the thermoplastic composition may besupplied (e.g., in the form of pellets) to a feed hopper attached to anextruder barrel that contains a rotating screw (not shown). As the screwrotates, the pellets are moved forward and undergo pressure andfriction, which generates heat to melt the pellets. Additional heat mayalso be supplied to the composition by a heating medium that iscommunication with the extruder barrel. One or more ejector pins 24 mayalso be employed that are slidably secured within the second mold half14 to define the mold cavity 16 in the closed position of the apparatus10. The ejector pins 24 operate in a well-known fashion to remove amolded part from the cavity 16 in the open position of the moldingapparatus 10.

A cooling mechanism may also be provided to solidify the resin withinthe mold cavity. In FIG. 1, for instance, the mold bases 12 and 14 eachinclude one or more cooling lines 18 through which a cooling mediumflows to impart the desired mold temperature to the surface of the moldbases for solidifying the molten material. Due to the uniquecrystallization properties of the thermoplastic composition, the“cooling time” during a molding cycle can be substantially reduced whilestill achieving the same degree of crystallization. The cooling time canbe represented by the “normalized cooling ratio”, which is determined bydividing the total cooling time by the average thickness of the moldedpart. As a result of the present invention, for example, the normalizedcooling ratio may range from about 0.2 to about 8 seconds permillimeter, in some embodiments from about 0.5 to about 6 seconds permillimeter, and in some embodiments, from about 1 to about 5 seconds permillimeter. The total cooling time can be determined from the point whenthe composition is injected into the mold cavity to the point that itreaches an ejection temperature at which it can be safely ejected.Exemplary cooling times may range, for instance, from about 1 to about60 seconds, in some embodiments from about 5 to about 40 seconds, and insome embodiments, from about 10 to about 35 seconds.

In addition to minimizing the required cooling time for a molding cycle,the method and composition of the present invention can also allow partsto be molded at lower temperatures while still achieving the same degreeof crystallization. For example, the mold temperature may be from about50° C. to about 120° C., in some embodiments from about 60° C. to about110° C., and in some embodiments, from about 70° C. to about 90° C. Suchlow mold temperatures may be accomplished using cooling mediums that areless corrosive and expensive than some conventional techniques. Forexample, liquid water may be employed as a cooling medium.

As a result of the injection technique employed in the presentinvention, it has been discovered that the thermoplastic composition canbe readily formed into parts having a small dimensional tolerance. Forexample, the thermoplastic composition may be molded into a part for usein an electronic component. The part may be in the form of a planarsubstrate having a thickness of about 100 millimeters or less, in someembodiments about 50 millimeters or less, in some embodiments from about100 micrometers to about 10 millimeters, and in some embodiments, fromabout 200 micrometers to about 1 millimeter. Alternatively, the part maysimply possess certain features (e.g., walls, ridges, etc.) within thethickness ranges noted above. Examples of electronic components that mayemploy such a molded part include, for instance, cellular telephones,laptop computers, small portable computers (e.g., ultraportablecomputers, netbook computers, and tablet computers), wrist-watchdevices, pendant devices, headphone and earpiece devices, media playerswith wireless communications capabilities, handheld computers (alsosometimes called personal digital assistants), remote controllers,global positioning system (GPS) devices, handheld gaming devices,battery covers, speakers, camera modules, integrated circuits (e.g., SIMcards), etc.

Wireless electronic devices, however, are particularly suitable.Examples of suitable wireless electronic devices may include a desktopcomputer or other computer equipment, a portable electronic device, suchas a laptop computer or small portable computer of the type that issometimes referred to as “ultraportables.” In one suitable arrangement,the portable electronic device may be a handheld electronic device.Examples of portable and handheld electronic devices may includecellular telephones, media players with wireless communicationscapabilities, handheld computers (also sometimes called personal digitalassistants), remote controls, global positioning system (“GPS”) devices,and handheld gaming devices. The device may also be a hybrid device thatcombines the functionality of multiple conventional devices. Examples ofhybrid devices include a cellular telephone that includes media playerfunctionality, a gaming device that includes a wireless communicationscapability, a cellular telephone that includes game and email functions,and a handheld device that receives email, supports mobile telephonecalls, has music player functionality and supports web browsing.

Referring to FIGS. 2-3, one particular embodiment of an electronicdevice 100 is shown as a portable computer. The electronic device 100includes a display member 103, such as a liquid crystal diode (LCD)display, an organic light emitting diode (OLED) display, a plasmadisplay, or any other suitable display. In the illustrated embodiment,the device is in the form of a laptop computer and so the display member103 is rotatably coupled to a base member 106. It should be understood,however, that the base member 106 is optional and can be removed inother embodiments, such as when device is in the form of a tabletportable computer. Regardless, in the embodiment shown in FIGS. 2-3, thedisplay member 103 and the base member 106 each contain a housing 86 and88, respectively, for protecting and/or supporting one or morecomponents of the electronic device 100. The housing 86 may, forexample, support a display screen 120 and the base member 106 mayinclude cavities and interfaces for various user interface components(e.g., keyboard, mouse, and connections to other peripheral devices).Although the thermoplastic composition of the present invention maygenerally be employed to form any portion of the electronic device 100,for example for forming the cooling fan, it is typically employed toform all or a portion of the housing 86 and/or 88. When the device is atablet portable computer, for example, the housing 88 may be absent andthe thermoplastic composition may be used to form all or a portion ofthe housing 86. Regardless, due to the unique properties achieved by thepresent invention, the housing(s) or a feature of the housing(s) may bemolded to have a very small wall thickness, such as within the rangesnoted above.

Although not expressly shown, the device 100 may also contain circuitryas is known in the art, such as storage, processing circuitry, andinput-output components. Wireless transceiver circuitry in circuitry maybe used to transmit and receive radio-frequency (RF) signals.Communications paths such as coaxial communications paths and microstripcommunications paths may be used to convey radio-frequency signalsbetween transceiver circuitry and antenna structures. A communicationspath may be used to convey signals between the antenna structure andcircuitry. The communications path may be, for example, a coaxial cablethat is connected between an RF transceiver (sometimes called a radio)and a multiband antenna.

The thermoplastic composition may forms components for otherapplications as well. For example, one component that may incorporate amolded part of the present invention is a liquid pump (e.g., waterpump). The liquid pump may be a direct lift pump, positive displacementpump (e.g., rotary, reciprocating, or linear), rotodynamic pump (e.g.,centrifugal), gravity pump, etc. Rotodynamic pumps, in which energy iscontinuously imparted to the pumped fluid by a rotating impeller,propeller, or rotor, are particularly suitable. In a centrifugal pump,for instance, fluid enters a pump impeller along or near to the rotatingaxis and is accelerated by the impeller, flowing radially outward into adiffuser or volute chamber, from which it exits into the downstreampiping. Such pumps are often used in automotive applications to move acoolant through the engine. Due to the high temperatures associated withautomotive engines, the thermoplastic composition of the presentinvention is particularly well suited for use in the centrifugal pumpsof such automotive cooling systems. In certain embodiments, for example,all or a portion (e.g., blades) of the water impeller may be formed fromthe thermoplastic composition of the present invention. Centrifugalpumps also generally include a housing that encloses certain componentsof the pump and protects them from heat, corrosion, etc. In someembodiments, some or all of the housing may be formed from thethermoplastic composition of the present invention.

Referring to FIG. 4, one particular example of a centrifugal pump isshown that can employ the thermoplastic composition of the presentinvention. In the illustrated embodiment, the pump contains a rotaryshaft 201 supported on a housing 203 via a bearing 202. A pump impeller204, which may contain the thermoplastic composition of the presentinvention, is rigidly fixed at an end of the rotary shaft 201. A pulleyhub 205 is also rigidly fixed on the base end portion of the rotaryshaft 201. Between the bearing 202 and the pump impeller 204, amechanical seal 206 is formed that is constituted by a stationary member206 a fixed on the side of the housing 203 and a rotary member 206 bfixedly engaged with the rotary shaft 201. The pump may also include ahousing 207, which can contain the thermoplastic composition of thepresent invention. The housing 207 may be affixed to the pump housing203 (e.g., with fastening bolts) so that a volute chamber 208 is definedtherebetween. While not illustrated, a suction portion and a dischargeport may also be provided within the housing 207.

Of course, the thermoplastic composition is not limited to the formationof water pumps or portions thereof, and it may be utilized in formingall manner of components as may be incorporated in a fluid handlingsystem including pipes and sections of pipes, flanges, valves, valveseats, seals, sensor housings, thermostats, thermostat housings,diverters, linings, propellers, cooling fans, and so forth.

The present invention may be better understood with reference to thefollowing examples.

Test Methods

Melt Viscosity:

The melt viscosity is determined as scanning shear rate viscosity anddetermined in accordance with ISO Test No. 11443 (technically equivalentto ASTM D3835) at a shear rate of 1200 s⁻¹ and at a temperature of 316°C. using a Dynisco 7001 capillary rheometer. The rheometer orifice (die)had a diameter of 1 mm, a length of 20 mm, an L/D ratio of 20.1, and anentrance angle of 180°. The diameter of the barrel was 9.55 mm+0.005 mmand the length of the rod was 233.4 mm.

Thermal Properties:

The thermal properties are determined by differential scanningcalorimetry (“DSC”) in accordance with ISO Test No. 11357. Under the DSCprocedure, samples are heated and cooled at 20° C. per minute as statedin ISO Standard 10350 using DSC measurements conducted on a TA Q100Instrument. For both pellet and mold samples, the heating and coolingprogram is a 2-cycle test that begins with an equilibration of thechamber to 25° C., followed by a first heating period at a heating rateof 20° C. per minute to a temperature of 320° C., followed byequilibration of the sample at 320° C. for 1 minutes, followed by afirst cooling period at a cooling rate of 20° C. per minute to atemperature of 50° C., followed by equilibration of the sample at 50° C.for 1 minute, and then a second heating period at a heating rate of 20°C. per minute to a temperature of 320° C. The results are evaluatedusing a TA software program, which identifies and quantifies the meltingtemperature, the endothermic and exothermic peaks, and the areas underthe peaks on the DSC plots. The areas under the peaks on the DSC plotsare determined in terms of joules per gram of sample (J/g). For example,the heat of fusion of a resin or mold sample is determined byintegrating the area of the endothermic peak. The area values aredetermined by converting the areas under the DSC plots (e.g., the areaof the endotherm) into the units of joules per gram (J/g) using computersoftware. The exothermic heat of crystallization is determined duringthe first cooling cycle and the second heating cycle. The percentcrystallization potential may also be calculated as follows:% crystallization potential=100*(A−B)/A

wherein,

A is the sum of endothermic peak areas (e.g., 1st heat of fusion); and

B is the sum of exothermic peak areas (e.g., pre-crystallization heat offusion).

Tensile Modulus, Tensile Stress, and Tensile Elongation:

Tensile properties are tested according to ISO Test No. 527 (technicallyequivalent to ASTM D638). Modulus and strength measurements are made onthe same test strip sample having a length of 80 mm, thickness of 10 mm,and width of 4 mm. The testing temperature is 23° C., and the testingspeeds are 1 or 5 mm/min.

Flexural Modulus, Flexural Stress, and Flexural Strain:

Flexural properties are tested according to ISO Test No. 178(technically equivalent to ASTM D790). This test is performed on a 64 mmsupport span. Tests are run on the center portions of uncut ISO 3167multi-purpose bars. The testing temperature is 23° C. and the testingspeed is 2 mm/min.

Izod Notched Impact Strength:

Notched Izod properties are tested according to ISO Test No. 180(technically equivalent to ASTM D256, Method A). This test is run usinga Type A notch. Specimens are cut from the center of a multi-purpose barusing a single tooth milling machine. The testing temperature is 23° C.

Deflection Under Load Temperature (“DTUL”):

The deflection under load temperature is determined in accordance withISO Test No. 75-2 (technically equivalent to ASTM D648-07). A test stripsample having a length of 80 mm, thickness of 10 mm, and width of 4 mmis subjected to an edgewise three-point bending test in which thespecified load (maximum outer fibers stress) is 1.8 MPa. The specimen islowered into a silicone oil bath where the temperature is raised at 2°C. per minute until it deflects 0.25 mm (0.32 mm for ISO Test No. 75-2).

Flash:

To determine flash, the sample is initially dried at 135° C. for 3 to 4hours. The sample is then injection molded into a dual tab flash moldusing the following conditions: melt temperature of 321° C., injectiontime of 1.5 seconds, injection pressure of 30,000 psi, hold time andpressure of 10 seconds at 1,000 psi, and screw retraction time of 20seconds. More particularly, the sample is injected so that 0.5 inches ofone tab is filled in 1.5 seconds with resin and 0.75 inches of the othertab remains unfilled. After cooling, the flash of the parts is measuredwith a MediaCybernetics automated image analysis system.

Synthesis of N1,N4-diphenylterephthalamide Compound A

The synthesis of Compound A from terephthaloyl chloride and aniline canbe performed according to the following scheme:

The experimental set up consists of a 2 L glass beaker equipped with aglass rod stirrer coupled with an overhead mechanical stirrer. Dimethylacetamide (“DMAc”) (3 L) is added to the beaker and the beaker isimmersed in an ice bath to cool the system to 10-15° C. Then aniline(481.6 g) is added to the solvent with constant stirring, the resultantmixture is cooled to 10-15° C. Terephthaloyl chloride (300 g) is addedgradually to the cooled stirred mixture such that the temperature of thereaction is maintained below 30° C. The acid chloride is added over aperiod of one-two hours, after which the mixture is stirred for anotherthree hours at 10-15° C. and then at room temperature overnight. Thereaction mixture is milky white (a fine suspension of the product in thesolvent) and is vacuum filtered using a filter paper and a Buchnerfunnel. The crude product is washed with acetone (2 L) and then washedwith hot water (2 L). The product is then air dried over night at roomtemperature and then is dried in a vacuum oven 150° C. for 4-6 hours.The product (464.2 g) is a highly crystalline white solid. The meltingpoint is 346-348° C. as determined by differential scanning calorimetry(“DSC”).

Synthesis of N1,N4-diphenylisoterephthanalide Compound B

The synthesis of Compound B from isophthaloyl chloride and aniline isperformed according to the following scheme:

The experimental set up consists of a 2 L glass beaker equipped with aglass rod stirrer coupled with an overhead mechanical stirrer. DMAc (1.5L) is added to the beaker and the beaker is immersed in an ice bath tocool the solvent to 10-15° C. Then aniline (561.9 g) is added to thesolvent with constant stirring, the resultant mixture is cooled to10-15° C. Isophthaloyl chloride (350 g dissolved in 200 g of DMAc) isadded gradually to the cooled stirred mixture such that the temperatureof the reaction is maintained below 30° C. The acid chloride is addedover a period of one hour, after which the mixture is stirred foranother three hours at 10-15° C. and then at room temperature overnight.The reaction mixture is milky white in appearance. The product isrecovered by precipitation by addition of 1.5 L of distilled water andfollowed by is vacuum filtration using a filter paper and a Buchnerfunnel. The crude product is then washed with acetone (2 L) and thenwashed again with hot water (2 L). The product is then air dried overnight at room temperature and then dried in a vacuum oven 150° C. for4-6 hours. The product (522 g) was a white solid. The melting point is290° C. as determined by DSC.

Synthesis ofN4-phenyl-N1-[4-[[4-(phenylcarbamoyl)benzoyl]amino]phenyl]terephthalamideCompound E

The synthesis of Compound E from 4-amino benzanilide and terephthaloylchloride can be performed according to the following scheme:

The experimental setup consisted of a 1 L glass beaker equipped with aglass rod stirrer coupled with an overhead mechanical stirrer.4-aminobenzanilide (20.9 g) is dissolved in warm DMAc (250 mL)(alternatively N-methylpyrrolidone can also be used). Terephthaloylchloride (10 g) is added to the stirred solution of the diaminemaintained at 40-50° C., upon the addition of the acid chloride thereaction temperature increased from 50° C. to 80° C. After the additionof the acid chloride is completed, the reaction mixture is warmed to70-80° C. and maintained at that temperature for about three hours andallowed to rest overnight at room temperature. The product is thenisolated by the addition of water (500 mL) followed by vacuum filtrationfollowed by washing with hot water (1 L). The product is then dried in avacuum oven at 150° C. for about 6-8 hours, to give a pale yellowcolored solid (yield ca. 90%). The melting point by DSC is 462° C.

Synthesis of N1,N3,N5-triphenylbenzene-1,3,5-tricarboxamide Compound J

Compound J can be synthesized from trimesoyl chloride and anilineaccording to the following scheme:

The experimental set up consists of a 2 L glass beaker equipped with aglass rod stirrer coupled with an overhead mechanical stirrer. Trimesoylchloride (200 g) is dissolved in dimethyl acetamide (“DMAc”) (1 L) andcooled by an ice bath to 10-20° C. Aniline (421 g) is added drop wise toa stirred solution of the acid chloride over a period of 1.5 to 2 hours.After the addition of the amine is completed, the reaction mixture isstirred additionally for 45 minutes, after which the temperature isincreased to 90° C. for about 1 hour. The mixture is allowed to restovernight at room temperature. The product is recovered by precipitationthrough the addition of 1.5 L of distilled water, which is followed byis vacuum filtration using a filter paper and a Buchner funnel. Thecrude product is washed with acetone (2 L) and then washed again withhot water (2 L). The product is then air dried over night at roomtemperature and then is dried in a vacuum oven 150° C. for 4 to 6 hours.The product (250 g) is a white solid, and has a melting point of 319.6°C. as determined by DSC.

Synthesis of 1,3-Benzenedicarboxamide, N1,N3-dicyclohexyl-Compound O1

The synthesis of Compound O1 from isophthaloyl chloride and cyclohexylamine can be performed according to the following scheme:

The experimental set up consisted of a 1 L glass beaker equipped with aglass rod stirrer coupled with an overhead mechanical stirrer.Cyclohexyl amine (306 g) was mixed in dimethyl acetamide (1 L)(alternatively N-methylpyrrolidone can also be used) and triethyl amine(250 g) at room temperature. Next isopthaloyl chloride (250 g) wasslowly added over a period of 1.5 to 2 hours, to the amine solution withconstant stirring. The rate of addition of the acid chloride wasmaintained such that the reaction temperature was maintained less than60° C. After complete addition of the benzoyl chloride, the reactionmixture was gradually warmed to 85-90° C. and then allowed to cool toaround 45-50° C. The mixture was allowed to rest overnight (for at least3 hours) at room temperature. The product was recovered by precipitationthrough the addition of 1.5 L of distilled water, which was followed bywas vacuum filtration using a filter paper and a Buchner funnel. Thecrude product was then washed with acetone (250 mL) and washed againwith hot water (500 mL). The product (yield: ca. 90%) was then air driedover night at room temperature and then was dried in a vacuum oven 150°C. for 4 to 6 hours. The product was a white solid. The Proton NMRcharacterization was as follows: ¹H NMR (400 MHz d₆-DMSO): 8.3 (s, 2H,CONH), 8.22 (s, 1H, Ar), 7.9 (d, 2H, Ar), 7.5 (s, 1H, Ar), 3.7 (broad s,2H, cyclohexyl), 1.95-1.74 broad s, 4H, cyclohexyl) and 1.34-1.14 (m,6H, cyclohexyl).

Example 1

The components listed in Table 1 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with an 18 mmdiameter.

TABLE 1 Sample Components FORTRON ® Com- Com- Com- Com- 0205 PPS pound Apound B pound E pound J Sample (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)Control 100 — — — — 1 98.0 2.0 — — — 2 98.0 — 2.0 — — 3 98.0 — — 2.0 — 498.0 — — — 2.0

The thermal properties of pellets formed from Samples 1, 2, and 4 aredetermined, the results of which are set forth below in Table 2.

TABLE 2 Thermal Properties Pre- Pre- 1^(st) 1^(st) 2^(nd) 2^(nd) Re-Cryst Cryst Heat, Heat Heat, Heat Re- Cryst Melt Heat of Melt of Melt ofCryst Heat of Cryst MV Temp Fusion Temp Fusion Temp Fusion Temp FusionPotential Sample (poise) (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (° C.)(J/g) (%) Control 504 126.3 23.9 282.2 39.3 280.9 38.5 233.2 45.0 39 1494 122.9 19.1 281.4 45.3 279.6 44.8 231.8 43.5 58 2 470 123.0 24.8280.1 43.8 279.5 44.2 230.7 46.8 43 4 447 125.9 24.5 280.5 41.8 279.943.7 231.8 46.5 41

As indicated above, the addition of the aromatic amide oligomerincreased the crystallization potential and reduced the crystallizationtemperature (“Re-Cryst Temp”). Samples 1, 2, and 4 are also molded intoT-bars on a Mannesmann Demag D100 NCIII injection molding machine at amold temperature of 130° C. The thermal properties are tested, theresults of which are set forth below in Table 3.

TABLE 3 Thermal Properties Pre- Pre- 1^(st) 1^(st) 2^(nd) 2^(nd) CrystCryst Heat, Heat Heat, Heat Re- Re-Cryst Melt Heat of Melt of Melt ofCryst Heat of Cryst Temp Fusion Temp Fusion Temp Fusion Temp FusionPotential Sample (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (%)Control 107.7 9.0 285.8 42.3 282.1 38.7 207.7 43.8 78.8 1 105.6 3.7286.1 44.4 282.8 42.8 226.3 41.4 91.7 2 106.7 11.3 283.3 47.6 280.1 41.6212.8 45.3 76.2 4 107.1 6.8 282.5 45.3 280.3 40.7 203.3 43.0 85.0

Both pellet and molded samples exhibited an increased crystallizationpotential upon the addition of the aromatic amide oligomer. Themechanical properties are also tested, the results of which are setforth below in Table 4.

TABLE 4 Mechanical Properties Tensile modulus Tensile stress Tensilestrain Flex Flex stress Izod (1 mm/min) (5 mm/min) (5 mm/min) modulus at3.5% Notched DTUL Sample (MPa) (MPa) (%) (MPa) (MPa) (kJ/m²) (° C.)Control 3444 52.5 1.7 3539 118.7 4.1 109.4 1 3849 73.2 2.4 3847 124.93.9 113.5 2 3663 59.5 1.8 3716 — 3.4 101.8 4 3579 73.1 2.4 3707 124.83.3 104.7

Example 2

The components listed in Table 5 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with an 18 mmdiameter.

TABLE 5 Sample Components FORTRON ® 0205 PPS Compound A Compound ESample (wt. %) (wt. %) (wt. %) Control 100 — — 5 99.5 0.5 — 6 98.0 2.0 —7 97.0 3.0 — 8 98.0 — 2.0

Once formed, the samples are molded into T-bars on a Mannesmann DemagD100 NCIII injection molding machine. The mechanical properties aretested, the results of which are set forth below in Table 6.

TABLE 6 Mechanical Properties Tensile Tensile Tensile modulus stressstrain Flex Flex Izod MV (1 mm/min) (5 mm/min) (5 mm/min) modulus stressNotched DTUL Sample (poise) (MPa) (MPa) (%) (MPa) (MPa) (kJ/m²) (° C.)Control 504 3444 52.5 1.7 3539 118.7 4.1 109.4 5 522 3858 63.2 1.8 3847119.0 3.1 109.5 6 494 3849 73.2 2.4 3847 124.9 3.9 113.5 7 457 4006 73.42.3 3923 125.2 3.5 118.1 8 551 3817 59.5 1.7 3798 129.3 2.8 112.1

Example 3

The components listed in Table 7 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with an 18 mmdiameter.

TABLE 7 Sample Components Glass FORTRON ® Compound Compound BoronGlycolube Fibers 0205 PPS A E Nitride P Aminosilane (4 mm) Sample (wt.%) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) Control 59.3 — — —0.3 0.4 40.0 1 Control 59.1 — — 0.2 0.3 0.4 40.0 2 9 58.7 0.6 — — 0.30.4 40.0 10 58.5 0.6 — 0.2 0.3 0.4 40.0 11 58.1 1.2 — — 0.3 0.4 40.0 1258.1 — 1.2 — 0.3 0.4 40.0

The thermal properties of pellets formed from the samples aredetermined, the results of which are set forth below in Table 8.

TABLE 8 Thermal Properties Pre- Pre- 1^(st) 1^(st) 2^(nd) 2^(nd) Re-Cryst Cryst Heat, Heat Heat, Heat Re- Cryst Melt Heat of Melt of Melt ofCryst Heat of Cryst MV Temp Fusion Temp Fusion Temp Fusion Temp FusionPotential Sample (poise) (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (° C.)(J/g) (%) Control 2648 126.1 11.1 280.9 22.7 277.4 22.2 214.3 23.1 51.11 Control 2590 124.8 8.2 281.0 21.3 280.8 21.4 236.5 23.6 61.4 2 9 2756124.5 6.5 281.2 22.7 280.0 20.0 230.5 23.5 71.2 10 2740 122.7 10.3 279.924.1 280.1 22.1 237.3 24.5 83.3 11 2434 124.4 10.3 279.9 24.8 278.8 22.6230.4 23.5 58.8 12 2358 121.8 8.2 282.2 22.2 279.1 21.2 226.3 23.9 63.2

As indicated above, the addition of the aromatic amide oligomerincreased the crystallization potential of the composition. The pelletsare also molded into T-bars on a Mannesmann Demag D100 NCIII injectionmolding machine. The thermal properties are tested, the results of whichare set forth below in Table 9.

TABLE 9 Thermal Properties Pre- Pre- 1^(st) 2^(nd) Re- Cryst Cryst Heat,1^(st) Heat, 2^(nd) Re- Cryst Melt Heat of Melt Heat of Melt Heat ofCryst Heat of Cryst Temp Fusion Temp Fusion Temp Fusion Temp FusionPotential Flash Sample (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (° C.)(J/g) (%) (mm) Control 105.7 2.6 281.8 23.4 277.8 22.4 217.1 24.9 88.90.21 1 Control 105.0 3.2 281.2 23.7 281.2 21.9 239.9 24.5 86.4 0.17 2 9104.7 2.7 281.7 23.6 279.8 22.3 234.1 24.9 88.6 0.14 10 105.6 3.6 281.624.5 280.9 23.4 240.0 25.3 85.2 0.12 11 104.5 2.1 280.8 23.4 281.1 23.3239.9 24.4 91.1 0.19 12 104.4 3.2 281.8 23.3 279.1 21.6 230.6 25.3 86.10.20

As indicated, the samples containing the aromatic amide oligomer(Samples 9-12) exhibited a lower amount of flash than Control 1 (nonucleating agents). The mechanical properties are also tested, theresults of which are set forth below in Table 10.

TABLE 10 Mechanical Properties Tensile Tensile Tensile Flex modulusstress strain Flex stress at Flex Izod (1 mm/min) (5 mm/min) (5 mm/min)modulus 3.5% Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa) (MPa) (%)(kJ/m²) (° C.) Control 15,654 201.2 1.8 14,920 304.0 2.3 10.7 264.5 1Control 15,548 202.1 1.8 14,978 304.6 2.3 10.0 266.6 2 9 15,998 205.91.8 15,417 301.8 2.2 9.6 269.7 10 16,047 207.1 1.8 15,560 302.0 2.2 10.2266.7 11 15,858 200.9 1.8 15,326 291.0 2.1 9.0 269.7 12 15,710 199.9 1.815,269 283.2 2.0 9.2 268.0

Example 4

The components listed in Table 11 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with a 25 mmdiameter.

TABLE 11 Sample Components FORTRON ® FORTRON ® Boron Amino- 0202 PPS0203 PPS Compound Nitride Glycolube silane Glass Fibers Sample (wt. %)(wt. %) A (wt. %) (wt. %) P (wt. %) (wt. %) (4 mm) (wt. %) Control 59.3— — 0.3 0.4 40.0 3 Control 59.3 — 0.3 0.4 40.0 4 13 58.6 0.6 0.1 0.3 0.440.0 14 58.6 0.6 0.1 0.3 0.4 40.0 FORTRON ® Boron 2,2′- Amino- 0214 PPSCompound Nitride Dithiodibenzoic Glycolube silane Glass Fibers Sample(wt. %) A (wt. %) (wt. %) acid (wt. %) P (wt. %) (wt. %) (4 mm) (wt. %)15 58.1 0.6 0.1 0.5 0.3 0.4 40.0 16 57.6 0.6 0.1 1.0 0.3 0.4 40.0

The thermal properties of pellets formed from the samples aredetermined, the results of which are set forth below in Table 12.

TABLE 12 Thermal Properties Pre- Pre- 1^(st) 2^(nd) Re- Cryst CrystHeat, 1^(st) Heat, 2^(nd) Re- Cryst Melt Heat of Melt Heat of Melt Heatof Cryst Heat of Cryst MV Temp Fusion Temp Fusion Temp Fusion TempFusion Potential Sample (kpoise) (° C.) (J/g) (° C.) (J/g) (° C.) (J/g)(° C.) (J/g) (%) Control 2.171 120.6 12.2 282.9 26.9 279.6 23.5 223.927.0 54.7 3 Control 2.196 120.5 7.4 282.9 26.8 279.1 23.3 225.4 27.072.2 4 13 1.682 117.1 1.0 282.6 28.0 282.5 26.9 244.2 28.8 96.3 14 1.862117.9 2.1 282.5 28.5 282.4 26.9 244.2 27.9 92.8 15 2.326 121.7 8.3 280.124.5 281.0 23.3 238.9 25.7 66.1 16 1.053 122.8 6.0 281.0 26.6 282.5 24.8241.9 26.5 77.4

As indicated above, the addition of the aromatic amide oligomerincreased the crystallization potential of the composition. The pelletsare also molded into T-bars on a Mannesmann Demag D100 NCIII injectionmolding machine at 130° C. and 80° C. The thermal properties are tested,the results of which are set forth below in Tables 13 and 14.

TABLE 13 Thermal Properties on T-bars mold @ 130° C. Pre- Pre- 1^(st)2^(nd) Re- Cryst Cryst Heat, 1^(st) Heat, 2^(nd) Re- Cryst Melt Heat ofMelt Heat of Melt Heat of Cryst Heat of Cryst Temp Fusion Temp FusionTemp Fusion Temp Fusion Potential Flash Sample (° C.) (J/g) (° C.) (J/g)(° C.) (J/g) (° C.) (J/g) (%) (mm) Control 117.5 1.0 283.0 26.3 282.225.4 244.0 28.9 96.3 0.258 3 Control 117.6 0.7 283.3 25.7 280.7 24.1239.3 27.5 97.2 0.249 4 13 114.1 0.5 283.0 24.7 283.6 24.0 250.5 26.198.1 0.233 14 101.2 0.5 282.4 25.0 283.7 24.5 250.3 26.9 98.2 0.258 15118.9 0.0 282.7 22.4 283.6 22.8 245.3 24.5 99.8 0.289 16 100.7 1.2 283.324.8 284.4 24.8 248.7 27.4 95.2 0.186

TABLE 14 Thermal Properties on T-bars mold @ 80° C. Pre- Pre- 1^(st)2^(nd) Re- Cryst Cryst Heat, 1^(st) Heat, 2^(nd) Re- Cryst Melt Heat ofMelt Heat of Melt Heat of Cryst Heat of Cryst Temp Fusion Temp FusionTemp Fusion Temp Fusion Potential Flash Sample (° C.) (J/g) (° C.) (J/g)(° C.) (J/g) (° C.) (J/g) (%) (mm) Control 104.8 3.2 283.5 25.3 280.123.5 224.0 27.0 87.2 0.065 3 Control 106.9 1.7 283.6 24.1 280.4 22.9233.2 27.2 92.7 0.079 4 13 103.2 1.6 281.9 26.6 282.4 26.3 245.7 28.693.9 0.081 14 103.0 1.5 282.3 25.7 282.6 24.3 248.9 27.2 94.1 0.059 15107.1 2.2 281.5 24.0 281.4 22.5 239.7 25.1 90.6 0.040 16 104.4 2.4 282.725.3 283.2 23.5 243.2 24.9 90.4 0.004

As indicated, the samples containing the aromatic amide oligomer(Samples 13-16) showed higher crystallization potential and higherrecrystallization temperature, indicating a faster crystallizationprocess than Control 3 and Control 4. Samples molded at 80° C. exhibiteda lower amount of flash than sampled molded at 130° C., and thecrystallization potential was maintained above 90% in the presence ofthe aromatic amide oligomer. The mechanical properties are also tested,the results of which are set forth below in Tables 15 and 16.

TABLE 15 Mechanical Properties (at 130° C. mold) Tensile Tensile Tensilemodulus stress strain Flex Flex Flex Izod (1 mm/min) (5 mm/min) (5mm/min) modulus stress Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa)(MPa) (%) (kJ/m²) (° C.) Control 15,047 185.1 1.6 14,686 272.1 1.9 9.6271.2 3 Control 14,821 191.2 1.8 14,408 275.4 2.0 10.1 269.3 4 13 15,725184.9 1.5 15,309 267.7 1.8 10.7 272.4 14 15,678 190.5 1.7 14,863 273.22.0 9.4 271.0 15 14,808 175.5 1.8 14,043 251.5 2.0 7.3 262.4 16 14,908163.5 1.5 13,410 243.2 2.1 14.4 262.4

TABLE 16 Mechanical Properties (at 80° C. mold) Tensile Tensile Tensilemodulus stress strain Flex Flex Flex Izod (1 mm/min) (5 mm/min) (5mm/min) modulus stress Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa)(MPa) (%) (kJ/m²) (° C.) Control 14,337 181.1 1.8 13,530 261.7 2.1 9.9268.7 3 Control 14,345 182.5 1.8 13,891 262.3 2.1 10.2 267.1 4 13 15,402186.7 1.7 14,522 278.3 2.1 9.5 271.4 14 15,205 184.7 1.7 14,167 275.72.1 9.4 274.0 15 14,292 168.4 1.8 13,410 243.2 2.1 7.6 261.3 16 13,914154.5 1.6 13,227 234.7 2.0 13.9 266.9

Example 5

The components listed in Table 17 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with a 25 mmdiameter.

TABLE 17 Sample Components FORTRON ® Boron Amino- 0203 PPS Compound JNitride Glycolube P silane Glass Fibers Sample (wt. %) (wt. %) (wt. %)(wt. %) (wt. %) (4 mm) (wt. %) Control 59.3 — — 0.3 0.4 40.3 4 17 58.60.6 0.1 0.3 0.4 40.0

The thermal properties of pellets formed from the samples aredetermined, the results of which are set forth below in Table 18.

TABLE 18 Thermal Properties of Pellets Pre- Pre- 1^(st) 2^(nd) Re- CrystCryst Heat, 1^(st) Heat, 2^(nd) Re- Cryst Melt Heat of Melt Heat of MeltHeat of Cryst Heat of Cryst MV Temp Fusion Temp Fusion Temp Fusion TempFusion Potential Sample (kpoise) (° C.) (J/g) (° C.) (J/g) (° C.) (J/g)(° C.) (J/g) (%) Control 2.196 120.5 7.4 282.9 26.8 279.1 23.3 225.427.0 72.2 4 17 2.192 121.3 4.5 281.4 25.4 281.8 24.4 243.7 27.5 82.2

As indicated above, the addition of the aromatic amide oligomerincreased the crystallization potential of the composition. The pelletsare also molded into T-bars on a Mannesmann Demag D100 NCIII injectionmolding machine. The thermal properties are tested, the results of whichare set forth below in Table 19 and Table 14.

TABLE 19 Thermal Properties of T-bars Pre- Pre- 1^(st) 2^(nd) Re- CrystCryst Heat, 1^(st) Heat, 2^(nd) Re- Cryst Melt Heat of Melt Heat of MeltHeat of Cryst Heat of Cryst Temp Fusion Temp Fusion Temp Fusion TempFusion Potential Flash Sample (° C.) (J/g) (° C.) (J/g) (° C.) (J/g) (°C.) (J/g) (%) (mm) Control 117.6 0.7 283.3 25.7 280.7 24.1 239.3 27.597.2 0.249 4 17 106.9 1.9 283.1 23.7 283.5 22.4 244.1 25.0 92.0 0.196

As indicated, the samples containing the aromatic amide oligomer(Samples 17) showed higher recrystallization temperature, indicating afaster crystallization process than Control 4. Due to the fastercrystallization, the flash performance of Sample 17 is also better thanControl 4. The mechanical properties are also tested, the results ofwhich are set forth below in Table 20.

TABLE 20 Mechanical Properties Tensile Tensile Tensile modulus stressstrain Flex Flex Flex Izod (1 mm/min) (5 mm/min) (5 mm/min) modulusstress Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa) (MPa) (%)(kJ/m²) (° C.) Control 14,821 191.2 1.8 14,408 275.4 2.0 10.1 269.3 4 1714,891 167.4 1.3 15,602 281.97 1.9 11.1 272.1

Example 6

The components listed in Table 21 below are mixed in a Werner PfleidererZSK 25 co-rotating intermeshing twin-screw extruder with a 25 mmdiameter.

TABLE 21 Sample Components FORTRON ® Boron Glass Fibers 0203 PPSCompound Compound Nitride Glycolube Amino-silane (4 mm) Sample (wt. %) J(wt. %) O1 (wt. %) (wt. %) P (wt. %) (wt. %) (wt. %) Control 59.3 0.30.4 40 5 Control 59.1 0.2 0.3 0.4 40 6 18 58.6 0.6 0.1 0.3 0.4 40 1958.6 0.6 0.1 0.3 0.4 40 20 58.6 0.6 0.3 0.4 40

The thermal properties of pellets formed from the samples aredetermined, the results of which are set forth below in Table 22.

TABLE 22 Thermal Properties of Pellets Ash content Melt Viscosity Sample(wt. %) (kpoise) Control 5 41.35 2.397 Control 6 40.78 2.237 18 40.892.192 19 40.64 2.111 20 40.80 1.870

The mechanical properties are also tested, the results of which are setforth below in Tables 23 and 24.

TABLE 23 Mechanical Properties (at 130° C. mold) Tensile Tensile Tensilemodulus stress strain Flex Flex Flex Izod (1 mm/min) (5 mm/min) (5mm/min) modulus stress Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa)(MPa) (%) (kJ/m²) (° C.) Control 15129 185.33 1.57 15110 291.18 2.07 10271.7 5 Control 14983 197.53 1.76 14775 289.19 2.08 10.60 272.60 6 1814891 167.43 1.35 15078 282.65 1.97 11.10 272.10 19 15150 167.80 1.3115602 281.97 1.89 10.40 271.60 20 15176 150.46 1.12 15460 279.01 1.8810.90 268.00

TABLE 24 Mechanical Properties (at 80° C. mold) Tensile Tensile Tensilemodulus stress strain Flex Flex Flex Izod (1 mm/min) (5 mm/min) (5mm/min) modulus stress Strain Notched DTUL Sample (MPa) (MPa) (%) (MPa)(MPa) (%) (kJ/m²) (° C.) Control 15025 189.58 1.70 14658 291.55 2.2410.2 269.9 5 Control 151.70 186.74 1.62 14561 287.36 2.21 10.20 270.90 618 14731 166.73 1.40 14607 289.43 2.20 10.50 270.10 19 15004 188.51 1.6514936 292.33 2.18 10.60 270.70 20 14724 191.30 1.81 14372 280.22 2.2110.60 272.60

These and other modifications and variations of the present inventionmay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present invention. Inaddition, it should be understood that aspects of the variousembodiments may be interchanged both in whole or in part. Furthermore,those of ordinary skill in the art will appreciate that the foregoingdescription is by way of example only, and is not intended to limit theinvention so further described in such appended claims.

What is claimed is:
 1. A method for injection molding a thermoplasticcomposition, the method comprising: injecting a thermoplasticcomposition into a mold cavity, wherein the thermoplastic compositioncomprises a polyarylene sulfide and aromatic amide oligomer; cooling thethermoplastic composition within the mold cavity at a mold temperatureof from about 50° C. to about 120° C., wherein the normalized coolingratio is from about 0.2 to about 8 second per millimeter; and ejectingthe molded part from the mold cavity.
 2. The method of claim 1, whereinthe mold temperature is from about 70° C. to about 90° C.
 3. The methodof claim 1, wherein water is used as a cooling medium.
 4. The method ofclaim 1, wherein the aromatic amide oligomer has a molecular weight ofabout 3,000 grams per mole or less.
 5. The method of claim 1, thearomatic amide oligomer having the following general formula (I)

wherein, ring B is a 6-membered aromatic ring wherein 1 to 3 ring carbonatoms are optionally replaced by nitrogen or oxygen, wherein eachnitrogen is optionally oxidized, and wherein ring B may be optionallyfused or linked to a 5- or 6-membered aryl, heteroaryl, cycloalkyl, orheterocyclyl; R₅ is halo, haloalkyl, alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, or heterocyclyl; m is from 0 to 4; X₁ and X₂ areindependently C(O)HN or NHC(O); and R₁ and R₂ are independently selectedfrom aryl, heteroaryl, cycloalkyl, and heterocyclyl.
 6. The method ofclaim 5, wherein ring B is phenyl.
 7. The method of claim 5, whereinring B is naphthyl.
 8. The method of claim 1, wherein the aromatic amideoligomer has the following general formula (IV):

wherein, X₁ and X₂ are independently C(O)HN or NHC(O); R₅, R₆, and R₇are independently selected from halo, haloalkyl, alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl; m is from 0 to4; and n and p are independently from 0 to
 5. 9. The method of claim 8,wherein m, n, and p are
 0. 10. The method of claim 8, wherein R₆ and R₇are phenyl substituted with —C(O)HN— or —NHC(O)—.
 11. The method ofclaim 1, wherein the aromatic amide oligomer has the following generalformula (V):

wherein, X₁ and X₂ are independently C(O)HN or NHC(O); R₆, R₇, and R₈are independently selected from halo, haloalkyl, alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl; m is from 0 to4; and p and q are independently from 0 to
 5. 12. The method of claim11, wherein m is
 0. 13. The method of claim 1, wherein the oligomer isselected from the group consisting of the following compounds andcombinations thereof: Structure Name

N1,N4-diphenyl- terephthalamide

N1,N4-diphenyl- isoterephthalamide

N1,N4-bis(2,3,4,5,6- pentafluorophenyl) terephthalamide

N1,N4-bis(4- benzamidophenyl) terephthalamide

N4-phenyl-N1-[4-[[4- (phenylcarbamoyl) benzoyl]amino]phenyl]terephthalamide

N4-phenyl-N1-[3-[[4- (phenylcarbamoyl) benzoyl]amino]phenyl]terephthalamide

N1,N3-bis(4- benzamidophenyl) benzene- 1,3-dicarboxamide

N3-phenyl-N1-[3-[[3- (phenylcarbamoyl) benzoyl]amino]phenyl]benzene-1,3-dicarboxamide

N1,N3-bis(3- benzamidophenyl) benzene- 1,3-dicarboxamide

N1,N4-bis(4-pyridyl) terephthalamide

N1,N3-bis(4-phenylphenyl) benzene-1,3- dicarboxamide

N1,N3,N5-triphenyl- benzene-1,3,5- tricarboxamide

N1,N3,N5-tris(4- benzamidophenyl) benzene-1,3,5- tricarboxamide

N-(4,6-dibenzamido- 1,3,5-triazin-2- yl)benzamide

N2,N7-dicyclohexyl- naphthalene-2,7- dicarboxamide

N2,N6-dicyclohexyl- naphthalene-2,6- dicarboxamide

N1,N3,N5-tris(3- benzamidophenyl) benzene-1,3,5- tricarboxamide

N,N′-dicyclohexyl- isoterephthalamide

N,N′-dicyclohexyl- terephthalamide.


14. The method of c aim 1, wherein the oligomer isN1,N4-diphenylterephthalamide.
 15. The method of claim 1, whereinaromatic amide oligomers constitute from about 0.1 wt. % to about 8 wt.% of the composition.
 16. The method of claim 1, wherein the compositionfurther comprises boron nitride, an impact modifier, mineral filler,fibrous filler, organosilane coupling agent, lubricant, disulfide, or acombination thereof.
 17. The method of claim 1, wherein the compositionhas a crystallization potential of about 55% or more, as determined bydifferential scanning calorimetry in accordance with ISO
 10350. 18. Themethod of claim 1, wherein the composition has a crystallizationpotential of from about 75% to about 95%, as determined by differentialscanning calorimetry in accordance with ISO
 10350. 19. The method ofclaim 1, wherein the length of flash created during the injectionmolding is about 0.17 millimeters or less.
 20. The method of claim 1,wherein the length of flash created during the injection molding isabout 0.13 millimeters or less.
 21. The method of claim 1, wherein themolded part has a thickness of about 100 millimeters or less or containsa feature having a thickness of about 100 millimeters or less.
 22. Themethod of claim 1, wherein the composition further comprises boronnitride.